United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-87/013 May 1987
Project Summary
Stack Testing of the Mobile
Plasma Arc Unit
Mark Gollands, Edward Peduto, Joanna Hall, and Howard Schiff
The Plasma Arc System developed by
Pyrolysis Systems, Incorporated (PSI)
underwent an extensive trial burn pro-
gram in Kingston, Ontario, Canada. The
plasma arc reactor with ancillary equip-
ment was designed as a mobile unit for
the highly efficient destruction of liquid
hazardous waste. Product gases from
the pyrolysis reaction are scrubbed and
then flared for the final destruction of
any remaining hazardous constituents.
The objectives of this program were
to evaluate the performance of the sys-
tem and to establish its destruction and
removal efficiency (ORE) while pyro-
lyzing both RCRA and TSCA regulated
hazardous wastes. In February 1985,
the system was operated over a two-
week period while introducing a liquid
waste containing CCI4. This effort was
essentially repeated in February 1986
when a liquid waste containing PCBs
was introduced to the system. The
emissions were sampled and analyzed
for: carbon tetrachloride (CCI4), hy-
drogen chloride (HCI), polychlorinated
biphenyls (PCBs), polychlorinated
dibenzo-p-dioxins (PCDD), polychlori-
nated dibp - "-.ans (PCDF), and par-
ticulate matter. Of notable concern were
polynuclear aromatics (PNAs), oxides
of nitrogen (NOX) and carbon monoxide
(CO) emissions. Samples of the scrubber
water generated were also analyzed for
CCI4, HCI, PCBs, PCDD/PCDF, and
PNAs. The system was evaluated during
two separate efforts.
During the CCI4 trial burns, the
pyrolysis system met the established
RCRA requirement with a DRE for
CCI4 of greater than 99.99 percent.
The CCI4 emissions averaged 24.98 x
106 kg/hr with an average input of
63.0 kg CCI4/hr. HCI emissions
averaged 0.35 kg/hr. NOX and CO
emissions were 0.35 and 0.14 kg/hr,
respectively. CCI4 discharged through
the scrubber water averaged 6.21 x
10 B kg/hr.
Results of the PCB trial burns indicate
that the pyrolysis system destroyed the
PCBs to a level of greater than or equal
to 99.9999 percent DRE. PCB stack
emissions during the three test runs
ranged from Not Detected (ND) to 0.11
x 108 kg/hr with a system DRE of
greater than 99.9999 percent. PCDD
and PCDF stack emissions were in the
range of ND to 0.028 x 106 kg/hr
(PCDD) and 0.082 x 10 6 to 0.304 x
10 6 kg/hr (PCDF). HCI and paniculate
matter emissions averaged 0.0039 and
0.028 kg/hr, respectively. NOxand CO
emissions averaged 0.476 and 0.053
kg/hr, respectively. PCDDs were not
detected in the scrubber water dis-
charge; however, PCDFs were detected
in very small concentrations in only the
first test run. PCBs discharged in the
scrubber water ranged from ND to 93.1
x 10 6 kg/hr and PNA concentrations
in the ppb range were detected in both
the stack gas and the scrubber water.
This Project Summary was developed
by EPA's Hazardous Waste Engineering
Research Laboratory, Cincinnati, OH, to
announce key findings of the research
project that Is fully documented In a
separate report of the same title (see
Project Report ordering Information at
back).
Introduction
The U.S. Environmental Protection
Agency's Hazardous Waste Engineering
Research Laboratory (HWERL), Cincinnati,
Ohio, and the New York State Department
of Environmental Conservation (NYSDEC)
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established a Cooperative Agreement in
1982. The Agreement called for the con-
struction and testing of a mobile pilot-
scale plasma arc system for the high
efficiency destruction of hazardous waste.
The capacity of the system is nominally
designed to be four kilograms (8.8 pounds)
per minute, and to fit, with ancillary
equipment, in a 45-foot trailer. The con-
cept of the plasma arc is that it uses high
intensity energy with temperatures ap-
proaching 10,OOO°C to break bonds of
hazardous waste chemical molecules
down to the atomic state. The recombina-
tion of these atoms produces molecules
such as hydrogen, carbon monoxide,
carbon dioxide and hydrochloric acid. The
off-gases from the plasma system are
subsequently scrubbed to remove hydro-
chloric acid and flared to remove com-
bustibles. A multi-stage sampling program
was designed to characterize and quantify
emissions from the plasma arc unit in
addition to establishing its destruction
and removal efficiency capabilities.
In general, the approach taken for this
EPA/NYSDEC Cooperative Agreement
involves four phases of activity. The first
two phases were performed in Canada
with the cooperation of Canadian Federal,
Provincial and local authorities; the third
and fourth phases will be performed in
the State of New York. The total Coopera-
tive Program is as follows:
Phase I: Construction and shakedown
of the mobile plasma arc
system by the vendor, Pyro-
lysis Systems, Inc. (PSI)
Phase II: Performance testing of the
plasma system at the Kings-
ton, Ontario test site (GCA
involvement).
Phase III: Transportation, installation
and verification of system
performance at a site in New
York State.
Phase IV: Demonstration tests as de-
signed by NYSDEC for per-
mitting purposes at a New
York State hazardous waste
site.
Project Objectives
The primary objectives of the program
were to demonstrate the destruction
capabilities of the system on waste
materials containing chlorinated com-
pounds. The first series of tests in Phase
II used carbon tetrachloride as the chlori-
nated feed component and as the target
compound in the analyses. This series
was essentially a preliminary test run
which could prove the performance of
the system on a "difficult to destroy"
compound with a very low heat of com-
bustion. Upon the successful demonstra-
tion of compliance with state, provincial,
and Federal requirements, the next test
series involved introducing an Askarel
blend waste feed containing 12-14 per-
cent polychlorinated biphenyls (PCB) by
weight.
Phase II measurement activities were
conducted in accordance with the Quality
Assurance Project Plan. The purpose was
to obtain information on the effectiveness
of the plasma arc, scrubber, and flare
systems in destroying or removing the
compounds of interest in the waste feed
and to assess the reliability of system
components and the stability of destruc-
tion performance. The parameters mea-
sured in each of the two test series are
shown in Tables 1 and 2.
Test Facility
All Phase II sampling was conducted
on the grounds of the Royal Military
College in Kingston, Ontario, Canada.
The mobile plasma pyrolysis system, as
shown in Figure 1, was operated by
Pyrolysis Systems, Inc. (PSI). The plasma
reactor and ancillary equipment were
housed in a 45-foot, specially adapted
trailer, capable of being transported from
site to site. PSI was responsible for pro-
viding and preparing the synthetic waste
feed blends for the Subsequent testing.
Table 3 outlines the waste feed param-
eters from the two test series.
Carbon Tetrachloride Trial Burn
Sampling for CCI4 emissions was
conducted during Stage II, Test Series 1,
to determine the overall CCI4 destruction
and removal efficiency (ORE) of the sys-
tem. CCI4 was selected as the principal
organic hazardous constituent (POHC)
because its very low heat of combustion
suggests it is a difficult material to be
thermally destroyed, based on EPA's cur-
rent ranking guidance1; it is readily avail-
able, and it is relatively inexpensive.
Testing was initiated on February 16,
1985, after four days of plasma arc system
preparation and test equipment set up.
Results for the carbon tetrachloride and
hydrogen chloride gas test runs are pre-
sented in Table 4.
The waste feed blend of CCI4, methyl
ethyl ketone and methanol was introduced
at rates averaging 2.82, 2.26, and 2.83
liters per minute (L/min). These cor-
respond to CCI4 mass feed rates of 64.2,
60.6, and 64.2 kilograms per hour (kg/hr).
These figures were used in calculating
the destruction and removal efficiency
(ORE) of the system shown in Table 4.
Scrubber water samples were taken
and analyzed for CCI4 concentrations
which were then combined with scrubber
Table 1. Carbon Tetrachloride Sampling Parameters
Sampling point
Measurement parameter
Postflare product gas
Spent scrubber water
Waste feed
Reactor ash
02, CO, C02, HCI, NOX, CCI4, flue gas velocity and temperature
CCI4
Sample and archive
Sample if available and archive
Table 2. PCB Sampling Parameters
Sampling point
Measurement parameter*
Postflare product gas
Spent scrubber water
(Reactor ash)
Waste feed
O2, CO2, CO, NOX, HCI, paniculate matter semivolatiles, VOCs,
PCDDs/PCDFs, PCBs, TCBs flue gas velocity, temperature,
moisture
semi-VOCs, VOCs, TCBs, PCBs, PCDDs/PCDFs
if available
PCDDs/PCDFs, PCBs, TCBs
* VOCs = volatile organic compounds
PCDDs = polychlorinated dibenzo-p-dioxins
PCDFs = polychlorinated dibenzofurans
PCBs = polychlorinated biphenyls
TCBs = total chlorinated benzenes
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Flow Diagram
Off Gases to Flare
Water Separator
(Scrubber)
Waste Feed AC/DC j |
Rectifier^]
Cooling Water
Figure 1. Process schematic of the PSI plasma pyrolysis unit (from Pyrolysis Systems, Inc.)
Emergency
Carbon Filter
Gas Chromatograph-
Mass Selectivity Unit
Laboratory
Analysis
Equipment
Gas
Chromatograph
Scrubber Water
Discharge to Drain
Table 3. Waste Feed Parameters
Parameters
Carbon tetrachloride burns-2/85
CC/4, mass %
Feed flow rate. L/min
Specific Gravity, kg/L
CCI4 feed rate, mg/min
kg/hr
PCB Bums - 2/86
PCB, mass %
Feed rate, kg/min
PCB feed rate, kg/min
kg/hr
Run 1
35
2.82
1.08
1.07
64.2
14.3
2.10
0.30
18.0
Run 2
40
2.26
1.12
1.01
60.6
12.5
2.33
0.29
17.4
Run 3
35
2.83
1.08
1.07
64.2
12.8
2.20
0.28
16.8
Average
36
2.64
1.09
1.05
63.0
13.2
2.21
0.29
17.4
water flow rates to yield the CCI4 mass
discharged to the sewer. The concentra-
tions of CCI4 detected in the scrubber
water were 1.27, 5.47, and 3.26 ppb
(jug/L), respectively, for the three 1 -hour
tests. The mass discharge rates are pre-
sented in Table 4.
During the CCI4 waste feed burns,
samples of the postflare stack gas were
obtained and analyzed for HCI and CCI4.
In addition to these parameters, the stack
gas flow rate, temperature, and bulk gas
constituents (02, CO, C02 and NOX) were
monitored on a continuous basis.
During Run 1, hydrogen chloride gas
(HCI) was sampled at the preflare location
but was aborted after 20 minutes due to
plugging of the sample line by the high
carbon and moisture content of the gas
stream. This sample was invalidated. No
further testing was attempted at this
location after several f larebacks occurred,
causing safety concerns at this sampling
location. The concentrations of HCI found
in the stack gas were 137.7 and 247.2
milligrams per cubic meter (mg/m3) for
Runs 2 and 3, respectively.
The concentrations of CCI4 present in
the stack gas during Runs 1, 2, and 3
were below the detection limit of the
electron capture gas chromatograph
(GC/ECD) analytical instrument (less than
2 ppb). For the purposes of this report,
and the establishment of a reportable
ORE for the system while firing a CCI4-
containing waste feed, CCI4 emission
rates of 29.27 x 10'6, 22.79 x 1CT6, and
24.98 x 10"6 kg/hr were used in the
calculations. The DRE is calculated using
only the stack gas emission rate and does
not include CCI4 discharged in the
scrubber water. Therefore, the established
DREs for Runs 1, 2, and 3 are all greater
than 99.99 percent, assuming a detection
limit of less than 15 ppb (the next highest
calibration standard above the blank).
The test combustion data are sum-
marized in Table 5. As is the case with
most combustion sources, NOX and CO
are good indicators of combustion tem-
peratures and efficiency. During startup
and shutdown operations, the flare is
quite unstable due to the non-steady
reactor product gas supply. This is due to
the fact that, during startup, the reactor
requires a minimum time period to reach
equilibrium temperature. Because of the
instability upon startup, the system was
brought up to operating temperatures on
a waste feed containing nonchlorinated
compounds, such as methyl ethyl ketone
(MEK). Once online and up to tempera-
ture, the chlorinated waste was then
introduced. There was usually a slight
instability in the system as the new waste
entered the plasma as was evidenced by
changes in the postflare stack gas tem-
peratures and concentrations of 02, CO2,
and NOX. Generally, once system tem-
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Table 4. CCI4 Trial Burns — CCI4 and HCI Emissions
Run 1 Run 2
Run 3 Average
Date, 1985
Test duration, min
Waste Feed Parameters
Waste Feed Composition
CC/4, mass %
MEK/MeOH
Specific gravity kg/L
Waste Feed Flow Rate,
L/min
kg/min
CCI4 Feed Rate, kg/min
kg/hr
Scrubber Water Parameters
Discharge Flow Rate,
L/min
CCI4 Concentration,
CCI4 Discharge Rate,
kg/hr
Ib/hr
Stack Gas Parameters
Average Flow Rate, m3/mina
ft3/mina
Average Temperature, °C
°F
HCI Cone., mg/m3a
HCI Emissions, kg/hr
Ib/hr
CC/4 Cone., ppbc
CCI4 Emissions, kg/hr
Ib/hr
2/18
60
35
65
1.08
2.82
3.05
1.07
64.2
33
1.27
2/26
60
40
60
1.12
2.26
2.53
1.01
60.6
30
5.47
2/26
60
35
65
1.08
2.83
3.06
1.07
64.2
32
3.26
60
36
64
1.09
2.64
2.88
1.05
63.0
32
3.33
2.51xW'6 9.85xW'6 6.26xW'6 6.21xW6
5.54x10'6 21.71xW'6 13.80x10'6 13.68x106
38.13
1,346.3
908
1,666
N/A
N/A
29.69
1,048.3
821
1.510
138
0.25
0.55
29.81
1,052.7
692
1,277
247
0.44
0.97
32.54
1,149.1
807
1.484
193
0.35
0.76
System CCI4 ORE.'
c c c c
29.27x10's 22.79x106 22.89x10'e 24.98x10'6
64.39xW'6 50.14x10'6 50.36x10'6 54.96x10'e
>99.99
>99.99
>99.99
>99.99
a Dry standard conditions as defined by 20°C and 760 mm Hg.
b HCI sampling conducted at preflare location. Sampling suspended due to carbon plugging of
train (not analyzed).
0 Results are based on estimated detection limit of 2 ppb. Actual detection limit was in the range
of 2-15 ppb and was not quantified.
peratures stabilized, CO concentrations
were relatively constant at a level of less
than 0.17 kg/hr.
PCB Trial Burn
In February 1985, three endurance PCB
trial burns were conducted. The waste
feed during these burns was comprised
of a blend of three Aroclors, trichloro-
benzene, methyl ethyl ketone, and
methanol. Askarel (Aroclor/trichloroben-
zene blend) comprised approximately 25
percent of the waste feed by weight. This
test series was included in the program
to test the plasma pyrolysis system over a
period of four hours while a waste of this
type was introduced.
Waste Feed — Askare
1/MEK/MEOH
The PCB waste feed blend was intro-
duced at an average rate of 2.21 kg/min
with a PCB mass input of 0.28 kg/min or
16.7 kg/hr. This mass input includes
monotnrough decachlorinated biphenyls.
Integrated samples were obtained during
each test run from the valving assembly
just prior to the feed ring of the reactor
vessel. At this point, the waste feed blenc
was well mixed and representative ol
that fed into the plasma reactor. The
samples were analyzed for total PCBs,
chlorobenzenes, polychorinated dibenzo-
p-dioxins (PCDDs), and polychlorinated
dibenzofurans (PCDFs).
Scrubber Water
Scrubber water samples were collectec
during each test run and analyzed foi
volatile and semivolatile compounds in-
cluding PCBs and PCDDs/PCDFs. Durinc
Runs 3-1, 3-2, and 3-3, scrubber watei
flow rate was 36.5,33.0, and 32.5 L/min
respectively.
The volatile compounds found in the
scrubber water were principally benzene
toluene, chlorobenzene, and styrene
Chloroethane and 2-butanone were alsc
found in Run 3-3 in measurable
quantities.
Generally, the semivolatile compounds
detected and quantified in the scrubbei
water are sister compounds to naphtha
lene and pyrene. The samples were two
phased, and the carbon layer typically
had higher concentrations of semivolatile
compounds than the aqueous phase. Ir
most cases, the carbon separated frorr
the aqueous solution, forming a top layei
with a light, meringue-type consistency
In other samples, the carbon remained ir
suspension or gradually settled out ovei
a period of time. This inconsistency ir
carbon layer formation may be due tc
varying consistency of the scrubber watei
in which the density of the carbon is
greater than that of the aqueous solutior
phase.
Split scrubber water samples were
analyzed by a second laboratory for PCB
PCDD, and PCDF content. In addition
Run 3-1 scrubber water samples were
analyzed for chlorobenzenes, chloro
phenols, and benzo (a) pyrene. PCDDs
were not detected in the scrubber watei
in any of the runs. PCDFs were detectec
in only the first run and mono through
decachlorinated biphenyls in the last twc
runs. Mono and dichlorinated biphenyl:
represented approximately 89 and 81
percent of the total PCB mass in Run;
3-2 and 3-3, respectively.
Postflare Stack Gas
Stack gas samples were collected dur
ing each run utilizing a variety of samplinc
trains and methods to obtain the require(
parameters. The stack gas constituent;
sampled for included 02, C02, CO, N0?
paniculate matter, HCI, volatiles, semi
volatiles, PCBs, and PCDDs/PCDFs. Alsc
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Table S. Combustion Parameters — CCI4 Trial Burns
Test run
1
Average
Date. 1985
Stack Gas Flow Rate, trf/min"
ft3/mina
Stack Gas Temperature, °C
°F
NOX Concentration, ppm (v/v)
Emission Rate, kg/hr
Ib/hr
CO Concentration, ppm (v/v)
Emission Rate, kg/hr
Ib/hr
02, percent
CO2, percent
2/18
38.13
1,346.3
908
1.666
106
0.46
1.02
48
0.13
0.28
12.7
6.0
2/26
29.69
1.048.2
821
1,510
92
0.31
0.69
57
0.12
0.26
14.4
5.7
2/26
29.81
1,052.7
692
1,277
81
0.28
0.62
81
0.17
0.37
15.1
4.9
32.54
1,149.1
807
1.484
93
0.35
0.78
62
0.14
0.30
14.1
5.5
' Dry standard conditions as defined by 20°C and 760 mm Hg.
included were measurements of gas
temperature, velocity, and moisture.
During the three operational periods in
which sampling runs 3-1, 3-2, and 3-3
were conducted, the postflare stack gas
was monitored for 02, CO2, CO, and NOX
using GCA's continuous emission moni-
toring system (CEMS).
Emissions of hydrochloric acid were
sampled at the postflare stack to deter-
mine stack gas concentrations as well as
the HCI mass emission rates. Concen-
trations in the gas stream were quite low
during all three runs averaging only 1.68
mg/m3 for an average emission rate of
64.1 mg/min or 0.0084 Ib/hr.
Paniculate emissions from the stack
show an average paniculate concentra-
tion of 0.005 grains per dry standard
cubic foot (gr/dscf) with an average
emission rate of 463.2 mg/min or 0.061
Ib/hr. Run 3-1 results were almost twice
as high as those from Run 3-2 or 3-3.
During Run 3-1, the stack gas tempera-
ture was much lower and the stack gas
flow rate was higher than the two sub-
sequent runs. System problems that led
to a shortening of Run 3-1 may also have
caused the increased grain loading (i.e.,
higher carbon concentrations in the re-
actor gas and postflare stack gas).
Sampling for semivolatile organics took
place during each test period using a
Modified Method 5 (MM5) sampling train
with an XAD sorbent module in place.
The semivolatile samples were analyzed
by GC/MS. As with the scrubber water
samples, the principal components found
were naphthalene and its sister
compounds.
A sampling train similar to the one
used for the collection of nonchlorinated
semivolatile organic compounds was used
to collect samples to be analyzed for
polychlorinated biphenyls (PCBs), poly-
chlorinated dibenzo-p-dioxins (PCDDs),
and polychlorinated dibenzofurans
(PCDFs). A destruction and removal ef-
ficiency (DRE) for the plasma pyrolysis
system when firing PCB-containing liquid
wastes was calculated for each run and
is presented in Table 6.
In calculating the DRE for PCBs during
Runs 3-2, and 3-3, an estimate of the
maximum possible PCB emission rate
had to be used for these runs because
the sample analyses yielded results
below the instrument detection Mmits.
Conclusions
Based on the test results and the
operatioal experience associated with
this test program, it can be concluded
that the technology shows promise as an
emerging technology which should be
further demonstrated. The data con-
tained herein are useful for engineering
research purposes and support the
conclusion that the technology shows
promise for future trial burn programs.
The further conclusions are focused on
the demonstration of an acceptable
destruction and removal efficiency as
delineated in the RCRA and TSCA
regulations.
• Results from the carbon tetrachloride
test burns indicate that the system is
capable of destroying "difficult to
destroy" compounds. The DREs from
each of the three test burns exceeded
the minimum RCRA requirement of
<99.99% destruction removal
efficiency.
• HCI emission rates conformed to the
allowable limits of <4 kg/hr and
<99% removal efficiency based on
inlet total chlorine content.
• Concentration of CCU in the scrubber
effluent ranged from 1.27-5.47 /ug/L
Effluent levels met the criteria for
discharge to the sewage treatment
plant.
• Results from the PCB test burns
indicate that the system is capable of
destroying a PCB liquid waste blend
consistent with the TSCA requirement
of >99.9999% DRE.
• HCI emission rates were again con-
sistent with the requirement of >4 kg/
hr and >99% removal efficiency based
on total chlorine input.
• High concentrations of polynuclear
aromatic hydrocarbon compounds
were detected in the two-phased
scrubber effluent. The predominant
species were naphthalene, ace-
naphthalene, phenanthrene, pyrene,
and fluoranthene Levels were in the
range of 12,000-72,000,ug/L Corres-
ponding levels in the flue gas dis-
charge were less than 245 /ug/m3.
• No appreciable levels of dioxin or
furan compounds (as total tetra
through octa) were detected in the
Table 6. Plasma Pyrolysis System DRE for PCBs3 in a Liquid Waste Feed
Date
2/12/86
2/20/86
2/22/86
Rune ft
3-1
3-2
3-3
Run duration
(min)
115
240
240
Waste feed rate
(kg/min)
2.10
2.33
2.20
PCB content
(% weight)
14.3
12.5
12.8
PCB mass
input (kg/hr)
18.018
17.475
16.896
PCB mass
out (kg/hrf
0. 1 1x1 0~6
<1.1x1Q-Sc
<1.1x1ffac
System DRE
percent
>99.9999
>99.9999
>99.9999
a Total PCBs as Mono (1) through Deca (10) polychlorinated biphenyls.
b PCB mass out does not include PCB mass discharged through scrubber water. Only stack emissions are used in the calculations.
c Concentrations of PCBs were below the instrument detection limits according to Zenon's analyses. In order to establish a minimum DRE, the sum of
their detection limits for Cl-1 — CI-10 was used to obtain a maximum possible emission rate.
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scrubber water. In all cases, levels
were eiother nondetectable or signif-
icantly less than 1 ng/L. Correspond-
ing levels in the flue gas were in the
ranges of 39.1-139 ng/m3 for the total
compounds and ND-12.6 ng/m3 for
the tetra-octa-chlorinated dibenzo-p-
dioxin.
Reference
1. "Presentation of a Method for the
Selection of POHCs in Accordance
with the RCRA Interim Final Rule,
Incinerator Standards," January 23,
1981, Off ice of Solid Waste.
Mark Go/lands. Edward Peduto. Joanna Hall, and Howard Schiff are with
Alliance Technologies Corporation (Formerly GCA Technology Division. Inc.),
Bedford. MA 01730.
C. C. Lee is the EPA Project Officer (see below).
The complete report, entitled "Stack Testing of the Mobile Plasma Arc Unit,"
(Order No. PB 87-152 450/AS; Cost: $13.95, subject to change) will be
available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Hazardous Waste Engineering Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
-------
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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